Benzyl hydroxy diphenyl polyglycol ethers



Patented Mar. 3, 1953 UNITED STATES OFFICE BENZYL HYDROXY DIPHENYL POLYGLYCOL ETHERS No Drawing. Application January 12, 1949, Serial No. 70,608. In Germany November 25, 1948 2 Claims. 1

The present invention relates to new polyglycol ethers of aromatic hydroxy compounds, which have proved to be excellent emulsifying and dispersing agents. The invention relates more particularly to polyglycol ethers of arcmatic hydroxy compounds containing at least three isocyclic rings. These new polyglycol ethers correspond to the following general formula:

In this formula Ar stands for a benzene nucleus or two condensed benzene nuclei, i. e. a naphthalene nucleus; R stands for an isocyclic radical, such as phenyl, cyclohexyl or benzyl; R1 stands for hydrogen or R; m means 1 or 2, and n means an integer from 6 to 30. In case Ar stands for a benzene nucleus R1 cannot be hydrogen but must necessarily be at least one of the R radicals in order to have three isocyclic rings in the compound. If R1 stands for R the radicals may be the same or difierent.

The new compounds can be obtained in known manner by reacting the substituted aromatic hydroxy compounds, 1. e. the substituted phenols or naphthols with ethylene oxide. For further details concerning the reaction see for example the U. S. Patents Nos. 2,213,477 and 1,970,578, as well as the German Patent No. 605,973. The starting materials, the substituted phenols and naphthols are likewise obtained in the usual known manner by condensing phenols or naphthols with the chloroderivates of the substituents in the presence of a Friedel-Crafts catalyst. Such condensation is described for example in the U. S.

Patent No. 2,213,477, Beilsteins Handbuch der Organischen Chemie, vol. 6, pages 583 and 675, vol. 6, 1st supplement, pages 295 and 324, vol. 6, 2nd supplement, pages 548-9 and 628-30, and Journal of the American Chemical Society, vol. 50, pages 2454 and following.

As examples for the substituted aromatic hydroxy compounds which may be used as starting materials the following may be mentioned: benzyl p-hydroxydiphenyl, benzyl o-hydroxydiphenyl, dibenzyl phenol, tribenzyl phenol, dibenzyl hydroxydiphenyl, benzyl naphthol, dicyclohexyl phenol, tricyclohexyl phenol, cyclohexyl phydroxydiphenyl, cyclohexyl o-hydroxydiphenyl,

cyclohexyl p-hydroxydiphenyl-methane, dicyclohexyl hydroxydiphenyl-methane, cyclohexyl naphthol. They are obtainable e. g. by condensing chlorobenzene, cyclohexyl chloride or benzyl chloride with phenol, hydroxydiphenyl or naphthol in the presence e. g. of aluminium chloride, zinc dust or any catalyst of similar action. Compounds such as cyclohexyl-benzyl-phenol may be obtained either by condensing cyclohexyl phenol with benzyl chloride or by condensing hydroxydiphenyl with cyclohexyl chloride. These starting materials may, of course, be further substituted e. g. by alkyl groups; thus e. g. instead of phenol a cresol may be used etc. It is further not necessary to use pure substituted aromatic hydrozq; compounds; also the technical mixtures may be used as they are obtained by the introduction of the substituents.

The number of ethylene oxide molecules combined with one molecule of the substituted aromatic hydroxy compounds depends on the intended use of the polyglycol ethers thus prepared and may vary between 5 and 30 molecules of ethylene oxide per one molecule of substituted aromatic hydroxy compounds; preferably 12 to 20 molecules of ethylene oxide are introduced into one molecule of the substituted aromatic hydroxy compounds, since the new polyglycol ethers built up in this ratio show excellent emulsifying and dispersing properties for the most purposes.

The new compounds are of oily to waxy consistency at room temperature. They are in water emulsifiable or soluble, depending on the number of ethylene oxide molecules introduced. By means of this new emulsifying and dispersing agents water-insoluble substances may be very finely dispersed or emulsified so that in many cases solutions are obtained which are almost optically clear. By this property the new compounds fundamentally differ from the emulsifying and dispersing agents hitherto used. This fact is very surprising, since polyglycol ethers of alkyl-substituted aromatic hydroxy compounds are Well known emulsifying and dispersing agents, and it was assumed that the capillary active properties of these compounds are promoted by longer also branched aliphatic radicals, while now these enhanced properties are obviously caused by the introduction of isocyclic substituents.

The new emulsifying and dispersing agents may be used in the most difierent fields of application. They may be used for the preparation of aqueous mineral oil emulsions; they may be applied in the textile industry. A further field of application is the emulsification of waterinsoluble pesticides which are to be applied in tion without limiting it thereto;.the-;partsheing;

by weight:

Example- 1 50 parts of benzyl p-hydroxydiphenyl';polyg-lyl.

col ether (prepared from'tlie distilled reaction product of benzyl chloride withp-hydroxydiphen yl and 16 mols of ethylene oxide) are-mixed with 50 parts of methylcyclohexa-nol. There is.- obtained a solution which clearly dissolvesiin .water: and is excellently suited for degreasing materials.

in aqueous solution. The mixture may'alsobe' used with advantage for cleaning textiles.

Example 2.

lllorparts of aawatereinsoluble organic com:- pound which; for instance, can .be :used'ia's insecticide; aresfinely pulverized: and mixed. with .15 parts of? benzyl' pehydroxydiphenyl. polyglycol ether (prepared-1 from the crude: reaction product of benzyl chloride with: p-hydroxydiphenyl; and. 1'7 molsof ethyleneoxide') withztheadditionof 1m) partsuof water. A fine-grained dispersion is 10btained which-can be easily distributeddn water and into which; for: instance; objects to be. treated are dipped: Bythis processtheactive, ezg. in:- seoticidal components are very finelysspread over the material, especially over textiles.

Example. 3

IOOErparts: of fultramarine are: groundin aball -mill with the. addition: of: 10.:partsz of benzyl' pchydroxydiphenyl polyglycol ether and. 100,. parts of? water:.. Anespecially. fine. dispersionoi: the pigmentzis-obtainedmhich is suitable. for painting 1' or: blueing textiles.

Example" 4 5.0-..parts: of; mineraloil, 50 parts: of-trainloil are mixedwhileadding; parts, of-- water; with 15 parts of benzyl o-hydroxydiphenylpolyglycol ether; (prepared; by: benzylation: of. o-hydroxydi phenyl according; to Friedel-Craftsand subsequent. reaction with :17. mols-.of: ethylene oxidev in theapresence .of:catalytic.quantities of NaOH') 'and the mixture thus; obtained is-emulsified by. adding itw-slowly; to.-.:waterr.while stirring... Awhite, .very

stable;emulsion;.isa-obtained, which can;p refer.-

Example 16 3.0-. partsgof oleiniare mixedwith 10-parts of dibenzyl. phenol. polyglycolether: (prepared by benzylation". of; phenol in the presence ofiiron1or aluminium :ch1oride:.and subsequentreaction with.

14 mols of ethylene oxide) and 10 parts of water, and this mixture is stirred with 45 parts of water yielding a white emulsion. This emulsion can be used in the textile industryin. greasing wool and has the advantage ofibeing readily wa'shed out again.

Example 7 100 partsofcarbon black are ground in a ball millwith 10 parts ofdibenzyl phenol polygylcol ether (prepared as described above) and 300 partsoftwater; Anon-settling carbon black dispersionis .formeds'which owing to its good penetrating property may preferably be used for staining Woodk.

A dispersionofpractically the same properties may-be obtained when using 10 parts of cyclohexyl [ii-naphthol' polyglycol ether (prepared by condensing fi-naphthol with chloroeyclohexane or cyclohexene and subsequent reaction with 16 mols of ethylene oxide) instead of dibenzyl phenol polyglycol ether. 7

Example 8. 10.0.parts.ofa-water-insoluble.organiccompound or a mixture. ofsuch compounds. which, for in stance, are; suitable as insecticides, are. liquefied either 'by-merel-y heating or; by. dissolving in 20-30 parts; of a; suitable organic solvent: and homogeneously mixed with -120 parts of a technical benzyl p-hydroxydiphenyl.polyglycol ether [prepared fromthe. crude: reaction product of parts of p-hydroxydiphenyl with*9() parts of benzyl chloride and subsequent reaction with about 3.00 parts-of; ethylene. oxide. The reaction product contains thepolyglycol' ethers of p-hydroxydiphenyll (about. 6%), benzyl p-hydroxydiphenyl (about 61%): and dibenzyl. p-hydroxydiphenyl (about 33%) 1. Thus stable, highly. concentrated insecticidal compositions are obtained-Which are clearly soluble. in. cold water and on applying them e; g; tovsurfaces dry. without leaving any visible residue... These compositions, therefore, can not only. be usedas insecticides in the usual manner but also for. combating pests in furnished rooms.

Example 9" 25 parts of cyclohexyl p-hydroxydiphenyl poly.- glycol ether (obtained; .for instance, by. condensing chlorocyclohexanei with ,.phydroxydiphenyl and subsequent treatment. with 18 :mols of ethyl.- ene oxide) are -mixed-with 75 partsof cyclohexanol. This solution-can-be diluted withwater to a clear: solution,. and: shows excellent cleaning properties for 'textilematerials.

100. partsof. titanium dioxideare ground. in a ballzmillfwith loparts ofcyc-lohexyl p-hydroxydiphenylemethane polyglycol ether (prepared, for instance, by condensing chlorocyelohexanew-ith pehydroxydiphenyl-methane and. subsequent rer actionwith 1'?- mols ,of ethylene. oxide .ors-byscon- (lensing o-cyclohexyl.a phenol. with b'enzyl chloride: and subsequent: treatment with ethylene oxide) and. 100. parts I of I water. The dispersion which isvery stable in water, may be used for painting purposes.

Example 12 100 parts of a water-insoluble organic compound or a mixture of such compounds as are, for instance, suitable as pesticides, are liquefied either by merely heating or by dissolving in to parts of a suitable organic solvent and homogeneously mixed with to parts of cyclohexyl o-hydroxydiphenyl polyglycol ether (prepared, for instance, by condensing chlorocyclohexane with o-hydroxydiphenyl and subsequent reaction of the distilled product with 16 to 17 mols of ethylene oxide). Thus stable, highly concentrated active compositions are obtained which are clearly soluble in cold water and dry up without leaving a visible residue when applied, for instance, to surfaces. These compositions, therefore, can be used not only for the combating of insects but also of pests in furnished rooms.

Example 13 The emulsion being of oily to waxy consistency.

KURT HANS ERNST HANSEN. OTHMAR LUDWIG DRAPAL. KARL WILHELM I-IINTZMANN. RICHARD WEGLER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,176,834 Bruson Oct. 17, 1939 2,213,477 Steindorfi Sept. 3, 1940 2,291,528 Bruson July 28, 1942 2,297,728 Taylor Oct. 6, 1942 OTHER REFERENCES Fuson et al., "Organic Chemistry (1942), page 432, John Wiley and Sons, New York, N. Y. (Not available for photostatic copies.) 

1. POLYGLYCOL ETHERS OF AROMATIC HYDROXY COMPOUNDS CONTAINING AT LEAST THREE ISOCYCLIC RINGS CORRESPONDING TO THE GENERAL FORMULA 